JPS6138216B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention, in the form of the free acid, has the general formula It relates to a compound represented by In this formula, A is the following formula

[Formula] −(CH ₂ ) _a − or

means a residue of the formula, where a is a number of 1, 2 or 3, B ¹ is a hydrogen atom, a chlorine atom, a bromine atom, a nitro group, an acetylamino group, or optionally a methyl group, an ethyl group or a sulfamoyl group substituted with a phenyl group, B ² is a hydrogen atom or a chlorine atom, B ³ is a hydrogen atom or a hydroxysulfonyl group, or
B ¹ and B ² taken together are an ortho-fused benzo ring, X is a group -O- or -COO-, and B is a group -O
-, -COO- or

[Formula] E is a group -O- or

[Formula], L means a hydrogen atom, a _C1 - _C15 -alkyl group optionally substituted with a hydroxyl group, a phenylsulfonyloxyethyl group, or a phenyl group, and D optionally a chlorine atom, a bromine atom ,
A phenyl group substituted with a nitro group or a hydroxysulfonyl group, or a naphthyl group substituted with a hydroxysulfonyl group, ^R1 is a hydrogen atom, a chlorine atom, a bromine atom, a _C1 - _C4 -alkyl group, a _C1 -C ₄ -alkoxy group or nitro group, R ² is a hydrogen atom or a nitro group, R ⁸ is a hydrogen atom or a hydroxysulfonyl group, or R ¹ and R ² together are ortho-fused, optionally substituted by a nitro group means a benzo ring, and Z is where R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or a phenyl group optionally substituted with a chlorine atom or a hydroxysulfonyl group, R ⁵ is a hydrogen atom or a hydroxysulfonyl group, or R ⁶ and R ⁷ together refer to an ortho-fused benzo ring optionally substituted with hydroxysulfonyl groups, and the molecule has a total of three hydroxysulfonyl groups. The radical SO ₃ H of the compound of formula
and in a ring substituted by R ¹ and R ² . Residue D of the diazo component is derived from benzole or naphthalene series. Amines of the formula H ₂ N-A-BH are derived from benzolic and naphthalene series as homocyclic amines, 1,2- or 1,3-diamines, -hydroxyamines or -aminos as aliphatic amines. It is a carboxylic acid. Individual compounds of the formula _H2N -A-BH are, for example, as follows. 2-aminophenol, 4-chloro-2-aminophenol, 4- or 5-nitro-2-aminophenol, 4,6-dichloro-
2-aminophenol, 4-chloro-5-nitro-2-aminophenol, 2-aminobenzoic acid,
4-nitro-2-aminobenzoic acid, 2-aminobenzoic acid-5-sulfonic acid, 2-aminophenol-4-sulfonic acid, 2-aminophenol-4-
Sulfonic acid amide, 2-aminophenol-4-
Sulfonic acid phenylamide, 2-aminophenol-5-sulfonic acid dimethylamide, 4-chloro-2-aminophenol-6-sulfonic acid, 4-
Nitro-2-aminophenol-6-sulfonic acid, 5- or 6-nitro-2-aminophenol-4-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-1-naphthol- 5-sulfonic acid, 1-amino-6-nitro-2
-naphthol-4-sulfonic acid, 1-aminoethanol-2, 1-aminopropanol-2,1-
Aminopropanol-3, 2-aminoacetic acid, 2-
Aminopropionic acid, 3-aminopropionic acid,
2-Aminobutyric acid, aminosuccinic acid or 2-aminoglutaric acid, and ethylenediamine, 1,2-
or 1,3-propylenediamine, N-phenylethylenediamine, N-phenylpropylenediamine-1,2 or N-methylethylenediamine. Residue Z is a residue of an azo coupling component (H-Z-EH) having a hydroxyl group or an amino group that forms a complex compound at the position next to the coupling position, and is derived from pyrazole, benzole, or naphthalene. be done. Individual compounds of the formula H-Z-EH are, for example, as follows. 2-naphthylamine, 2-naphthol, 1-naphthol-5-sulfonic acid, 2-naphthol-6-sulfonic acid, 1-naphthylamine-4- or -5-sulfonic acid, 2-naphthylamine-5- or -6-sulfone acid, 3-methyl-5
-Pyrazolone, 1-phenyl-3-methyl-5-
Pyrazolone, 1-phenyl-5-aminopyrazole, 1-phenyl-5-pyrazolone-3-carboxylic acid, 1-(4'-chlorophenyl)-3-methyl-
5-pyrazolone, 1-(2',5'-dichlorophenyl)-3-methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone-3'- or -
4'-sulfonic acid, 1-(2'-chlorophenyl)-3
-Methyl-5-pyrazolone-5'-sulfonic acid or 1-(2',5'-dichlorophenyl)-3-methyl-
5-pyrazolone-4'-sulfonic acid. The benzole ring substituted by R ¹ and R ² contained in the general formula is an aniline derivative having a hydroxyl group or carboxyl group that forms a complex at the o-position with respect to the diazotizable amino group. Therefore, this aniline derivative is a homocyclic compound H ₂ N−
It corresponds to the type A-BH and may be the same or different. The individual compounds of the diazo component containing the residue D are in particular the following: Aniline, 2-, 3
- or 4-chloroaniline, 4-bromoaniline, 2,5-dichloroaniline, 4-acetylaminoaniline, 4-benzoylaminoaniline,
N-(4-aminophenyl)-oxamidic acid, 2
-, 3- or 4-nitroaniline, 2-chloro-
4-nitroaniline, aniline-4-sulfonic acid amide, aniline-3-sulfonic acid-N-phenylamide, 2-aminobenzoic acid, aniline-3-
or -4-sulfonic acid, 4-methylaniline-2
-Sulfonic acid, 2,5-dichloroaniline-4-
Sulfonic acid, 4-nitroaniline-2-sulfonic acid, 1-aminonaphthalene, 1-aminonaphthalene-4- or -5-sulfonic acid, 2-aminonaphthalene-5- or -6-sulfonic acid or 2-
Aminonaphthalene-4,8-disulfonic acid. In addition to a hydrogen atom, the residue L is, for example, the following. _C1 - _C6 -alkyl groups, _C2- or _C3 -hydroxyalkyl groups or phenyl groups. Preferred residues L are, for example, _C1 - _C4 -alkyl, β-hydroxyethyl or -propyl groups,
Or a phenyl group. The production of the 1:2-chromium complex is carried out stepwise via the 1:1-complex. For this we need the general formula producing a 1:1-chromium complex compound represented by
This is the general formula It is preferable to react with an arylazo-azomethine compound represented by the formula to produce a 1:2-chromium complex compound of the general formula. m and n in the formulas and mean the numbers 0, 1, 2 or 3, m+n=3, and the other symbols have the meanings given for the formulas. The preparation of the 1:1-chromium complexes takes place by known methods, in the case of o·o'-dihydroxyazo complexes the corresponding o-alkoxy-o'-
It is also possible to start from hydroxyazo compounds. The reaction of the 1:1-chromium complex of the formula with the arylazo-azomethine of the formula or its individual components is carried out in an aqueous solution or suspension, optionally in an organic solvent such as an alcohol, a glycol, a carboxylic acid amide or Particular preference is given to adding urea derivatives. The formation of the 1:2-complex compound is carried out in a weakly acidic to alkaline range, preferably from PH6 to 9.
and at an elevated temperature, for example 50° C. to boiling temperature. The 1:2 complex formed is isolated by acidification, salting out with alkali metal salts, evaporative concentration or spray drying. Choosing a suitable solvent or mixture thereof: 1:
The 2-chromium complex compounds can also be prepared in the form of stable concentrated solutions and can then be used directly in this form for the preparation of dyebaths or printing pastes. To prepare this dye solution, it is particularly advantageous to use a compound of the formula and in the form of the free dye sulfonic acid and to adjust the suitable PH number using an alkanolamine in a solvent. The 1:2-chromium complex compounds of the general formula are suitable for dyeing and printing or printing natural or synthetic nitrogen-containing materials, such as wool, leather, polyamide fibers or polyurethane fibers. The dyeings obtained are distinguished by high fastness properties, e.g. lightfastness, and in particular exhibit very good wet fastness properties, e.g. fastness to washing, shrinkage, perspiration and potting, these properties often being or better than similar known dyes having only two sulfonic acid groups.
It was unexpected that the dyes of the invention, despite their molecular size and the large number of anionic electrolytes, showed good migration ability and therefore gave uniform dyeings. Owing to their high solubility, the dyes are particularly suitable for continuous dyeing processes, such as the dyeing of carpets. 1:2-chromium complex compounds that are particularly important industrially are
general formula From the 1:1-chromium complex compound of the azo compound represented by the general formula It is obtained by combining with arylazo-azomethine represented by In formulas and R 10 , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a chlorine atom, a bromine atom, a nitro group or an acetylamino group, or R ⁹ and R ¹⁰
together mean an ortho-fused benzo ring, p, q and r mean the number 0, 1 or 2,
However, the total number of sulfonic acid groups in the generated 1:2-complex compound is 3. Example 1 A suspension of 15.3 parts of 5-phenylazo-2-hydroxybenzaldehyde-4'-sulfonic acid in 150 parts of water was dissolved in 4-chloro-2-aminophenol-6
- Heat to 50° C. with 11.4 parts of sulfonic acid and 12 parts of sodium acetate. After the azo-azomethine compound is formed, the diazotized 4-nitro-2-
An equimolar amount (approx.
26 parts) and heat to 70-80°C while stirring. At the same time, by adding caustic soda solution, 1:2
- Maintaining a PH value of 7-8 until the formation of the complex compound has ceased, and then evaporating or spray drying the solution gives 62 parts of a dye of the formula: λ _nax
( _H2O ): 404nm. This dye gives uniform yellowish-orange dyeings on wool and polyamide fibers with very good light and wet fastness properties. In the same way, the dyes shown in the following table are obtained.

【table】

[Table] Example 7 In 200 parts of water, 15.3 parts of 5-phenylazo-2-hydroxybenzaldehyde-4'-sulfonic acid,
11.8 parts of 4-chloro-2-aminophenol-6-sulfonic acid and diazotized 1-amino-
35.5 parts of a 1:1 chromium complex of an azo dye obtained from 2-naphthol-4-sulfonic acid and 1-phenyl-3-methyl-5-pyrazolone are suspended. Heat to 80°C with stirring and bring to pH 7.5 by adding caustic potash solution. After the formation of the 1:2-complex is completed, 180 parts of potassium chloride is added and the precipitated dye is isolated, yielding 79 parts of the complex of the following formula. λmax ( _H2O ): 440nm. This dyestuff dyes wool in a yellowish-red shade, and the dyeing has high fastness properties, in particular very good wet fastness properties. In the same way, the dyes shown in the following table are obtained.

【table】

[Table] Example 14 11.2 parts of 4-chloro-2-aminophenol-6-sulfonic acid and 15.5 parts of 5-phenylazo-salicylaldehyde-4'-sulfonic acid were mixed with di-(2-
Hydroxypropyl)-heat in 30 parts of ether and 40 parts of water to 50° C. for 30 minutes. The resulting azo-azomethine compound contains diazotized 1-amino-2
- Add 22.6 parts of a 1:1-chromium complex of an azo dye obtained from naphthol-4-sulfonic acid and 2-naphthol, and add 26.2 parts of 2-(dimethylamino)-ethanol dropwise at 70° C. while stirring. . 1:2
- When the formation of the complex compound is complete, dilution with water brings the total weight of the reaction mixture to 165 parts, giving an approximately 45% solution of the complex salt of the formula: λ _nax ( _H2O ):
576, 612nm. This solution is storage stable and, upon printing, gives an olive pattern on woven floor coverings made of wool and/or synthetic polyamide. In a similar manner, the dye solutions shown in the following table are obtained.

【table】

Table Example 20 15 parts of 5-phenylazosalicylaldehyde-4'-sulfonic acid are suspended in 300 parts of water and stirred with 8 parts of N-phenylethylenediamine at 50° C. for 30 minutes. After adding 30 parts of a 1:1-chromium complex compound of an azo dye obtained from diazotized 1-amino-2-hydroxynaphthalene-4-sulfonic acid and 1-hydroxynaphthalene-8-sulfonic acid, the mixture was heated to 80°C. Heat and keep at PH 7.5 until the formation of the complex compound ceases. After salting out with sodium chloride, 60 parts of a complex dye of the following formula are obtained. λ _na
x (H ₂ O): 519, 604, 652 nm. This dye gives a fast green dyeing on wool and synthetic polyamides. A similar method gives the dyes shown in the following table.

【table】

【table】

Claims (1)

[Claims] 1. In the form of a free acid, the general formula (In the formula, A means a residue of the following formula [Formula] - (CH ₂ ) _a - or [Formula], where a is a number of 1, 2 or 3, B ¹ is a hydrogen atom, a chlorine atom, a bromine atom) atom, a nitro group, an acetylamino group or a methyl group, a sulfamoyl group optionally substituted with an ethyl group or a phenyl group, B ² is a hydrogen atom or a chlorine atom, B ³ is a hydrogen atom or a hydroxysulfonyl group, or B ¹
and B ² taken together are an ortho-fused benzo ring, X is a group -O- or -COO-, and B is a group -O
-, -COO- or [Formula] E means the group -O- or [Formula], L is a hydrogen atom or a C ₁ -C ₁₅ -alkyl group or phenyl group which may be substituted with a hydroxyl group, D is a phenyl group A chlorine atom, a bromine atom, a phenyl group optionally substituted with a nitro group or a hydroxysulfonyl group, or a naphthyl group substituted with a hydroxysulfonyl group, R ¹
is a hydrogen atom, a chlorine atom, a bromine atom or a nitro group,
R ² means a hydrogen atom or a nitro group, R ⁸ means a hydrogen atom or a hydroxysulfonyl group, or R ¹
and R ² taken together mean an ortho-fused benzo ring optionally substituted with a nitro group,
And Z is the following formula where R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or a phenyl group optionally substituted with a chlorine atom or a hydroxysulfonyl group, and R ⁵ is a hydrogen atom or a hydroxysulfonyl group. , or R ⁶ and R ⁷ together,
(meaning an ortho-fused benzo ring optionally substituted with a hydroxysulfonyl group) and having a total of three hydroxysulfonyl groups in the molecule. 2 General formula A compound represented by the general formula (In these formulas, m and n mean the numbers 0, 1, 2, or 3, m+n is 3, and other symbols have the meanings given below.) In the form of the free acid, characterized by the general formula (In the formula, A means a residue of the following formula [Formula] - (CH ₂ ) _a - or [Formula], where a is a number of 1, 2 or 3, B ¹ is a hydrogen atom, a chlorine atom, a bromine atom) atom, a nitro group, an acetylamino group, or a sulfamoyl group optionally substituted with a methyl group, an ethyl group, or a phenyl group, B ² is a hydrogen atom or a chlorine atom, B ³ is a hydrogen atom or a hydroxysulfonyl group, or
B ¹ and B ² taken together are an ortho-fused benzo ring, X is a group -O- or -COO-, and B is a group -O
-, -COO- or [Formula] E means the group -O- or [Formula], L is a hydrogen atom or a C ₁ -C ₁₅ -alkyl group or phenyl group which may be substituted with a hydroxyl group, D is a phenyl group A chlorine atom, a bromine atom, a phenyl group optionally substituted with a nitro group or a hydroxysulfonyl group, or a naphthyl group substituted with a hydroxysulfonyl group, R ¹
is a hydrogen atom, a chlorine atom, a bromine atom or a nitro group,
R ² means a hydrogen atom or a nitro group, R ⁸ means a hydrogen atom or a hydroxysulfonyl group, or R ¹
and R ² taken together mean an ortho-fused benzo ring optionally substituted with a nitro group,
And Z is the following formula where R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or a phenyl group optionally substituted with a chlorine atom or a hydroxysulfonyl group, and R ⁵ is a hydrogen atom or a hydroxysulfonyl group. , or R ⁶ and R ⁷ together,
A method for producing a 1:2-chromium complex compound dye, which is represented by (meaning an ortho-fused benzo ring optionally substituted with a hydroxysulfonyl group) and has a total of three hydroxysulfonyl groups in the molecule.